Condensation product and method of preparing same.



my, li t i LAURENCE V. BEDMAN, OF CHICAGO, ILLINOIS, ASSIGNOR TO REDMANOL CHEMICAL PRODUCTS COMPANY, OF CHICAGQILLINOIS, CORPORATION OF WEST VIRGINIA.

CONDENSATION PRODUCT AND METHOD OF PREPARING SAME.

To all whom it may concern .Be it known that I, LAURENCE V. Brio- MAN, a citizen of the United States, resldmg at Chicago, in the county of Cook and State of Illinois, have invented a new and useful Condensation Product and Method of Preparing Same, of which the following is a specification.

- My invention relates particularly to condensation productsof phenol and substances containing the methylene radical, and

- methods for preparing same.

My primary object is to provide a product which is free from impurities, and further, to provide an improved process, enabling a substance of this character to be produced in an exceedingly simple manner, the process belng capable of being easily practised in a com- 'mercial Way and giving improved results.

An important object is to provide a practical process which will enable a compound of definite characteristics to be produced with the greatest certainty and under conditions possessing great practical advan tages. According to my improved process, I d1- rectly combine a phenolic body, such as carbolic acid, with hexamethy-lenetetramin by an anhydrous re-action carried on substantially in the absence of water, using an ex cess ofphenol, that is, more phenol than can combine with the methylene present in the hexamethylenetetramin to form a. final hard, insoluble, infusible product, thus obfinal product at a comparatively low tern:

perature and without the use of pressure; and I am able to obtain a product of great purity and possessing in the highest degree the many valuable characteristicsadesirable in this class of product. I am able, also, in

Specification of Letters Patent.

Patented June 20, 191%..

Application filed February 24, 1914. Serial No. 820,774..

the practice of the process, to dispensewith the use of catalyzers and to avoid the necess1ty of removing such substances, or attempt ing .to neutralize the harmful efi'ects of such substances in the product.

According to my preferred method, I first obtain a fusible condensation product of phenol and hexamethylenetetramin in the following manner: Mix phenol and hexamethylene'tetramin in the proportions of- 1 mol. of hexamethylenetetramin to 11 mols. of phenol and heat the same to a temperature of approximately 130 C. The application of heat is then discontinued, and the dilute alkalis, phenol, and other solvents. After the nitrogen or the most of it has been driven oif as ammonia, the mass-is allowed --to cool to a temperature of approximately 105 (1., when it appears as a thick, quite viscous liquid of amber yellow color, where we substances are used, or'of darker color, if crude phenol be used.

As an illustration of the step followed in producing the fusible condensation product, the following may be stated: I may take 103 pounds carbolicacid (CJ-LOI-I), mix

the same with 14; pounds of hexamethylenetetramin' ((GH,),N,) otherwise known as formin, heat the same to a temperature of approximately 130 (1, discontinue the ,ap-

plication of heat, allowing the mass to become automatically heated to a temperature of 180 C., With continuous evolution of ammonia after the temperature rises above 140 (3.; when the evolution of ammonia abates, again apply heat and boil briskly at approximately 183 0., for such period as may be necessary to drive off the most of the nitrogen, a period of five hours usually suflicing for this operation.

The foregoingstep is carried on substantially in the,absence..of water, and gives an anhydrous re-action. The substance may mulanow -be represented by the following forabout 62% of z H, 0011 0 11 OOH C HQH (phenyl-endeka-saligeno-saligenin) and 38 7 of C I-I QH (phenol).

, insoluble, infusible following steps, viz

Having. produced the fusible phenolic resin whidh is substantially an anhydrous product without impurities, such as catalyzers ,or salts produced in an effort to neutralize the effects of catalyzers, I'may proceed to convert the substanceto the final product by either of the (a) Allow the fusible, phenolic resin to cool to about 105C although cooling temperatures as high as 120 C. may be employed,-dissolve it 'in a 40% solution of for- Imaldehyde (formalin), using 15 pounds of CH O,which would be represented by about 38 pounds (about 4.7 gallons) of the solution; mix with the resin thus'dissolved about .466 pounds hexamethylenetetramin; then allow the mass to cool to, or, if necessary, maintain it at a temperature of approximately 65 C.- although this temperature may vary until hardening takes place.

, L When the fusible resin is dissolved in the manner abovestated, the substance may be" poured into moldsand introduced into ovens and gradually dried at a temperature of approximately 65 C., the hardening taking place in the molds; and the material may be removed 1 from the molds as soon as the hardening is accomplished. It is found that, following. this method of procedure to obtain the final product, a very slight shrinkage takes place in the hardening,

which facilitates removal of the substance from the mold.

(b) The, step of converting the fusible resin to the finalproduct maybe carried on in themanner-just described, except that instead of the A66 poundhexamethylenetetramin, there may be substituted ,4 pound of solution of ammonia (28% solution).

- (0) Instead of using formalin to effect the conversion to the final product, I may use 11.66 pounds of hexamethylenetetramin dissolved in a mixture of 50% alcohol and 50% Water, or dissolved in formalin as a saturated solution, or in any mixture of the ordinary alcohols and water, or any mixture of alcohols and formalin, or any mixture of acetone and water, or any other suitable solvent, which, if desired, maybe in pure form, such as any alcohol. The manner of eifecting the conversion to the final product is similar to the step described at The substance will be found tocontain' rom or thereabout downward (d) Stop the heat while some nitrogen is still retained in the fusible resin, allow the mass .to'cool to 105- 0., and then add a sufficient amount of a methylene compound to effect conversion of the substance to the final insoluble state, corresponding with the union of six mols. of phenol with six groups of active methylene (furnished, for instance, by 1 .mol. of hexamethylenetctramin), the' temperature being preferably maintained at about 65 C. while the hardening takes place. In some instances, however, as in producing steam-packings or valves, it is desirable to use a temperature approximating 180 C. inthe finalportion of the treatment. 4

In each instance,'I employ, to effect the conversion to the final product, a substance in effecting theconversion to the, final state.

In such case, the solution of formalin may be employed without the addition of hexamethylenetetramin. Following this method of effecting conversion to. the final state, I

am able to-produce a transparent product,

glass-like in appearance, or having almost water-white color, if desired.

It is to be borne in mind, generally speaking, that the color is apt to vary with the variation in the purity of the material to be used. For illustration, if one uses crude phenol, the product will have'a darker color; and one may use dyes (coal tar dyes, if desired), and produce various colors. In fact, the color may vary from ahnost a colorless appearance to a dark amber, a dark ruby, or

even a black color.

. Where it is desirable to produce trans.-

parent effects, the second step of the process described at (a) is desirable; and Where it is especially desirable to produce the highest grade of an insulation product, the second step in the process described at (c) is desirable, avoiding the use of any considerable percentage of water in the final step of the process.

It will be noted as a characteristic of the improved process that in the first step of the process the serious difliculties which have so long been experienced in this art by the practice of the old Wet formaldehyde process, with the attendant difficulties incident to the use of large quantities of Waterand necessary catalyzers during this stage of producing a phenolic condensation product, are entirely obviated; and at the end of the first step of the process, the product is left in a sufficiently mobile state to render easy the succeeding step of converting the substance to the final infusible state. Not only so, but the method followed renders it possible to eliminate the ammonia in the easiest possible manner, producing a fusible, anhydrous resin, which requires no other treatment than that of permitting cooling preparatory to introducing the methylenes necessary to efiect the conversion to the final state, and finally gives aproduct of the greatest purity. 7

It is to be noted that the proportions may be varied somewhat. For illustration, I

I may state that in the first step of-the process I have demonstrated that 'with 1 mol. of hexamethylenetetramin I may use phenol ranging from approximately 9 mols. to approximately 13 mols., but 11 mols. give the best result. Again, while it is preferred to use practically pure materials, it may be necessary commercially to use the commercially obtainable ingredients. Thus, the phenol may, without great detriment, contain a small amount of water, say in the neighborhood of 5%. As indicated, however, the anhydrous material is desirable.

It thus will be seen that in the first step of the process I re-act upon a phenolic body with an anhydrous methylene body, compounded in the proportions affording more than 1 phenol group toone methylene group.

Indeed, within the lowest limit of the range within which I have practised the improved process, I employed approximately 1?; phenol groups to .an active methylene group,

' while within the highest limit I use "more than two phenol groups to one active methylene group. In producing the final product for lnsulation purposes," I may, preparatory to the final step of the process, introduce fillers, such as kieselguhr, ground silica,

' powdered slate, stone, asbestos, wood fiber,

cellulose, or the like.

It is an especially valuable feature of the process that the conversion of the fusible resin to the final inf'usible state can be effected at low temperature and without the use of pressure. This is highly desirable for many purposes, and is peculiarly desirable when the product is to be used as a coating, or as a varnish, particularly when applied to articles which maybe injured by heating at high temperature, .or by prolonged heating. In the practice of the final step of the process, they material may be applied as a' coating, and the drying may be efiected at low temperature, the conversion to the final product being efi'ected during the drying process.- I

Instead of using carbolic acid, one may employ a homologue, such as the cresols, or any other suitable commercially obtainable phenolic body. So also, any substance which will serve'as a substitute for the hexamethylenetetramin to supply the methylene in an anhydrous re-action carried on in the absence of water, may be employed in the first step of the process.

It may be stated here that hexamethylenetetramin is a methylene-main derivative, containing both the methylene group and nitrogen, or the constituents of ammonia. The use of such a derivative is desirable in producing the anhydrous fusible resin in the first step of the process herein described.

In the practice of the first step of the process, the ammonia evolved may be 001- lected and discharged into a solution of fomaldehyde to produce fresh hexamethylenetetramin; and this, in turn, may be used in the practice of the process. The initial product may be rapidly and economically produced; and the final product may be produced under the most advantageous conditions. The final product corresponds, as nearly as can be determined, with a union of .1 mol. of hexamethylenetetramin to 6 mols. of phenol.

It may be added that while it is preferred to allow the material to cool somewhat after the first step of the process, with a View to.

securing a more quiescent re-action in the second step of the process, nevertheless the second step of the process may he proceeded with without first allowing the material to cool; and it may be stated generally that the application of heat may be regulated throughout to secure vthe best results for the particular purpose in view. The feature of producing the first anhydrous soluble resin by. anhydrous re-action between a .phenolic body and a methylene body compounded in proportions to leave a comparatively largeamount 'of free phenol in the resin, and finally adding a methylene body in suflicient quantity to convert the soluble product to the final insoluble state, is one of the utmost importance, but capable, nevertheless, of being carried out with a considerable range'of variation in specific decondensation product, the step which consists in mixing a phenolic body and an active methylene body in the proportions of considerably more than 1 phenol group to each active methylene group of the methylene body; and subjecting the same to the action methylene group; heating. the mixture sub-' stantially in the absence of water to .a temperature of approximately 130 C. to cause an anhydrous reaction; substantially discontinu-ing the application of heat and allowing the temperature of the mass to rise to approximately 180 C. with the evolution of ammonia; and applying further heat when theevolution'of ammonia abates, the application of heat being continued and the temperature maintained at approximately 180 C. till the most of the nitrogen is driven off from the mass.

3, In a process of producing a phenolic condensation product, the step which consists in mixing a phenolic body and hexamethylenetetramin in the proportions of considerably more than 1 phenol group to 1 methylene group; heating the mixture substantially in the absence of water to a temperature of approximately 130 C. to cause an anhydrous reaction; substantially discontinuing the application ofheat and allowing the temperature of the mass to rise to approximately 180 C. with the evolution of ammonia; applying further heat when the evolution of ammonia abates, the application of heat being continued and the temperature maintained at approximately 180 C. till substantially all of the nitrogen is driven oif from the mass; and allowing the mass to cool to a temperatureof approximately 105 0.

4. The. process of producing an infusible,

insoluble condensation product, which consists in combining hexamethylenetetramin r with a phenolic bodyby an anhydrous reaction-in substantially the absence of water, the materials being used in the proportions of considerably more than 1 phenol group to 1 methylene group, the substance being initially heated to a degree sufiicient to cause automatic heating of the mass to take place;

allowing the automatic heating to continue,

while the external heating isabated, until the evolution of ammonia abates; then apply- "ing external heat to drive off mostiof the remaining nitrogeng then cooling the mass to i a temperature below.120' (3.; then converting the mass to the final insoluble infusible product by introducing a substance containing-the temperature of the mass to be automatically raised to about 180 C., with evolution of ammonia, the artificial heat being abated during this period; applying further artificial heat when the evolution of ammonia abates, and boiling the mass briskly for a prolonged period, thereby driving ofi the most of the remaining nitrogen, thus obtaining phenyl endeka saligeno saligenin with a free phenol incorporated therein.

6. The process of producing a fusible condensation product, which consists in compounding a phenolic bodyand hexamethylenetetramin in the proportions to afford at least substantially 11} phenol groups to 1 methylene group; heating the mixture sufficiently to cause automatic heating to occur; abating'the application of heat and allowing the mass to rise in temperature to approximately 180 C., with evolution of ammonia; and applying further heat, when the evolution of ammonia abates, to drive oif most of the remaining nitrogen in the product.

7. The process of producing an insoluble, infusible condensation product, which consists in compounding a phenolic body and hexamethylenetetramin in proportions to art-- ford more than 1% phenol groups to 1 methylene group; raising the temperature by heat from an external source to such a point that automatic heating will occur; abating the heat from the external source while automatic heating continues with evolution of ammonia; applyingmore external heat when the evolution of ammonia abates,

and -maintaining'the temperature at about 180 C. for a prolonged period till most of the remaining nitrogen is driven off allowing the product to cool; and finally introducing a substance containing sufiicient methylene to convert the product to the final infusible, insoluble state, and efi'ectmg such conversion at a still .further reduced temperature.

ble condensation product, the steps which conslst 1n comblning, by anhydrous re-action in substantially the absence of water, a'

the nitrogen or the mixture, thus producing 130 8. In the process of producing an infusimeaoia bining, by an anhydrous re-action in substantially the absence of water, a phenolic body, and a methyleneamin body, compounded in proportions of more than 19 phenol groups to 1 methylene group, sufficient external heat being applied to drive off substantially all the nitrogen of the mixture, thus producing a fusible condensation product containing more than of-free phenol; cooling the fusible resin to a point below 120 0.; incorporating with the cooled resin a substance containing sufficient methylene to convert the resin to the final insoluble state and slowly cooling the product; and applying further heat at comparatively low temperature till conversion to the final state is effected.

10. In the process of producing an insoluble, infusible condensation product, the steps which consist in compound ng a phenolic .body and hexamethylenetetramin in proportions which will furnish considerably more than 1 phenol group to 1 methylene group; applying external heat sufficient ducing to substantially drive off the nitrogen. and

produce a fusible condensation product containing free phenol; allowing the mass to cool to a point below 120 (l; and introingredients containing a small amount of nitrogen and a sufficient large quantity of a methylene-carrying body to convert the product to the insoluble state.

11. The process of producing an insoluble, infusible condensation product, which consists in compounding a phenolic body and hexamethylenetetramin in proportions which will furnish considerably more than 1 phenol group to 1 methylene group; applying external heat suflicient to substantially drive off the nitrogen .and produce a fusible condensation product containing free phenol; allowing'themass to cool'to a point below 120 (1.; introducing ingredients containing a small amount of nitrogen and a sufficiently large quantity of a methylene-carrying body to convert the:

product to the insoluble state; and heating the product at .a relatively low temperature till the conversion to the final state ,is effected.

12. lhe'process of producing an infusible, insoluble condensation product, which consists 1n re-acting on a phenolic body with hexamethylenet etramin, taken in propor nitrogen, thus producing a fusible condensation product'containing more than 25% free phenol; and finally introducing a substance containing sufficient methylene groups to convert the fusible resin to the final infusible product and causing the conversion to the final product to take place at a temper ature below 7 5 C.

13. The process of producing an infusible, insoluble condensation product, consisting. in causing an anhydrous re-action substantially in the absence of water, between a phenolic body and an anhydrous methylene body containing an amin group in proportions furnishing considerably more than 1 phenol group to 1 active methylene group; applying sufficient heat to substantially drive off the ammonia, thus producing an anhydrous, fusible resin; lowering the temperature of the resin, and dissolvingthe resin in a solution of formaldehyde; and drying and hardening the product.

14. The process of producing an infusible, insoluble condensation product, consisting in causing an anhydrous re-action suba it stantially in the absence of water between a phenolic body and an anhydrous methylene body containing an amin group in proportions furnishing more than 1 phenol group to. 1 active methylene group; applying sufficient heat to substantially driye off the ammonia, thus producing an anhydrous, fusible resin; lowering the temperature of the resin and dissolving the resin in a. solution of formaldehyde; introducing a small per- .centage of hexamethylenetetramin; and drying and hardening the product.

15. In the process of producing a phenolic condensation product, the step which consists in mixing a phenolic body and a methylene-amin derivative in the propor,

tions of considerably more than one phenol ,1 group to each active methylene group of the methylene-amin derivative; and subjecting the same to the action of heat substantially in the absence of water and causing an anhydrous reaction, to produce a fusible phenolic resin. Y

16. As a new composition of matter, the fusible, "anhydrous resinous condensation product containing a. high percentage of free phenol and produced by combining in an anhydrous re-action, substantially in the absence of water, an active methylene body and a phenolic body in proportions fur-" nishing considerably-more than 1 phenol group to 1 active methylene group.

17. In the art of producing condensation products, the process of producing an intermediate fusible product, which :consists in compounding a phenolic body and hexa-' methylenetetramin, substantially in the ab-.

sence' of water, in such" proportions as to afford. at least 1% phenol groups substantlally to one methylene group; and heating 1W the mixture and driving ofl:' the most of the nitrogen in the form of ammonia.

18. The process of producing an infusible condensation product, which consists in combining, by anhydrous re-action in substantially the absence of Water, a phenolic body and hexamethylenetetramin compounded in proportions of at least 1% phenol groups to one methylene group; applying suflicient heat to drive off most of the nitrogen, thus producing a fusible condensation product containing more than 25% of free phenol; and incorporating with the fusible resin a substance containing sufiicient methylene groups to convert the resin into the final insoluble state, and continuing the heat treatment until the insoluble product results.

"19. The process of producing an infusible,

H insoluble condensation product, Which consists in re-acting on a phenolic body with hexamethylenetetramin in an anhydrous reaction, said bodies taken in proportion affording at least one and one-fourth phenol groups to 1 methylene group, applying sufiicient heat to drive off most of the nitrogen,

thus producing a fusible condensation prodv V. REDMAN. In presence of- A. C. Frsonnn,

NELLIE VB. DEARB ORN. 

